利用OH自由基特征发射谱测量正庚烷的点火延迟时间

在化学激波管中利用反射激波进行点火,采用OH自由基在306.4nm处特征发射谱线强度的急剧变化标志燃料的着火,由光谱单色仪、光电倍增管、压力传感器和示波器组成测量系统,测量了正庚烷/氧气的点火延迟时间,点火压力(1.0±0.1)和(0.75±0.05)atm,点火温度1 170～1 730K,当量比1.0,得到了在此实验条件下正庚烷/氧气点火延迟时间随温度变化的关系式。研究结果表明正庚烷/氧气点火延迟时间随温度的增加呈指数减小,点火压力为0.75atm时,随着点火温度的增加,点火延迟时间的变化率要小于1.0atm条件时。实验结果为建立正庚烷燃烧反应动力学模型,验证正庚烷燃烧反应机理提供了实验依据。     

发射光谱法研究甲基环己烷燃烧时激发态自由基时间历程

采用三组单色仪探测系统,测量了甲基环己烷在高温反射激波作用下瞬态燃烧反应过程中三种激发态自由基OH*,CH*和C*₂的特征光辐射,得到了激发态自由基时间历程和光辐射相对强度随温度的变化规律。反射激波温度1 200～1 700 K,激波压力1.5 atm,甲基环己烷摩尔分数0.1%,当量比1.0。在点火燃烧初始阶段三种自由基几乎同时产生,自由基持续时间随着温度的升高而变短。相同温度下CH*和OH*自由基持续时间大于C*₂自由基,在1 400 K以下C*₂自由基发光消失。OH*和CH*自由基发光强度在T<1 400 K时对温度变化不敏感,而在T>1 400 K时CH*自由基峰值随温度快速增长,C*₂和OH*峰值随温度增大比较平缓。将实验结果和化学反应机理模拟结果进行了对比,实验获得的OH*自由基时间历程在低温时和机理预测结果吻合较好,但在高温时有一定差异。CH*自由基时间历程在高温与机理结果吻合较好,在低温时机理预测结果CH*自由基持续时间要长于实验结果。实验测得的结果为含激发态物种化学反应动力学机理的验证和优化提供了依据。     

正癸烷燃烧反应中OH,CH和C2自由基的瞬态发射光谱

采用ICCD瞬态光谱测量系统和加热激波管,在点火压力2.0atm,点火温度1 100～1 600K,当量比1.0,燃料摩尔分数1.0%条件下,实时测得了正癸烷/氧气/氩气燃烧过程的瞬态发射光谱,光谱范围200～850nm。结果显示燃烧过程中主要发射光谱带归属于小分子中间产物OH,CH和C2自由基,光谱强度的变化反映了燃烧过程中三种自由基浓度的变化历程;正癸烷燃烧过程中光谱强度峰值之比大于同为链烷烃的正庚烷相应OH/CH峰强度之比,揭示出两种链烃燃烧反应机理有较大差异。实验还获得了正癸烷燃烧过程中能显示谱带转动结构的CH和C2高分辨特征发射光谱。实验结果对了解正癸烷燃烧性质和验证正癸烷燃烧反应机理很有意义。     

正庚烷燃烧反应中间自由基的光谱测量

采用ICCD瞬态光谱探测系统和化学激波管,在点火温度1 408K,点火压力2.0atm,燃料摩尔分数1.0%,当量比1.0的条件下,拍摄了正庚烷燃烧过程中不同时刻的瞬态发射光谱,光谱曝光时间6μs,拍谱范围200～850nm。确认了在所拍光谱范围内主要是OH,CH和C2自由基的特征辐射光谱,表明小自由基OH,CH和C2是正庚烷燃烧过程中重要的反应中间产物。所拍时间分辨光谱显示,在正庚烷燃烧反应中,OH,CH和C2自由基一出现很快就达到其浓度峰值,但CH和C2自由基随着反应的进行迅速减少至消失,OH自由基持续的时间却长很多。实验结果为了解正庚烷燃烧反应微观过程和验证其燃烧反应机理提供了实验依据。     

苯快速反应点火特性的光谱研究

利用由单色谱仪、压力传感器以及示波器组成的测试系统,测定了高温激波管中苯快速反应的几个重要产物:H,C2和CH的点火延迟时间和出现的顺序.提出了一种在入射激波条件下确定含能材料冲击点火延迟时间的新方法,并介绍了苯在快速反应中碳生成的微观反应机理.研究表明:无论马赫数如何改变,H原子总是最先出现,说明苯在快速反应过程中,首先断裂的C-H键,而不是C-C键.利用较早出现的反应中间产物H原子来测定苯的点火延迟时间更为准确.利用单色谱仪技术能较好地研究苯的快速反应点火特性,新方法与国内外常用的全色光技术相比可明显减少实验量.     

瞬态发射光谱法研究正十二烷燃烧反应特性

采用加热激波管和增强型CCD瞬态光谱测量系统,在波长范围200~900nm,点火压力4.0atm,点火温度(1 200~1 300)K,当量比0.5、1.0和2.0的条件下,实时测得了正十二烷/空气和正十二烷/氧气/氩气燃烧过程的瞬态发射光谱.结果表明:燃烧过程在此波段内的主要发射光谱带归属于反应中间产物OH、CH和C2自由基;在不同当量比条件下,燃烧过程中OH(306.4nm)/CH(431.4nm)/C2(516.4nm)的光谱强度显著不同,贫油情形有利于OH自由基生成,富油情形有利于C2自由基生成;浴气的不同会导致燃料燃烧温度的不同,从而引起燃料燃烧发射光谱的不同.所测燃烧反应自由基的时间分辩光谱直观反映出正十二烷燃烧过程中重要中间产物OH、CH和C2的变化情况.研究结果有助于认识正十二烷燃烧反应特性和验证其燃烧反应机理.     

戊二烯快速反应点火特性的光谱研究

采用ＯＭＡⅢ光多道谱仪、单色谱仪及作者研制的相关测试技术,研究了高温激波管中戊二烯快速反应光谱和点火延迟时间。研究表明：利用各种谱仪技术能较好地研究易挥发燃料的快速反应点火特性。利用谱仪技术所确认的较早出现的反应中间产物来测定的点火延迟时间,与国内外常用的全色光技术进行了比较。     

超声速预混可燃气流的点火与燃烧

在激波风洞一激波管组合设备上开展了碳氢燃料超声速预混可燃气流的点火与燃烧实验研究。实验结果表明:利用激波对燃料进行预热,并以高温燃气作为引导火焰,可以有效缩短汽油空气超声速可燃混气的点火延迟时间,使之缩短到 0.2 ms以下。利用纹影照片对超声速燃烧流场结构作出了分析;研究了超声速预混可燃气流的温度以及当量比对超声速燃烧流场结构、点火与火焰传播特性的影响。     

铝粉对己烷与氧混合物快速反应发射光谱的影响

观察高温激波管中己烷与氧气在不同摩尔比下加入不同粒度铝粉前后的快速反应发射光谱。整个光辐射范围从４００ｎｍ一直延伸到探测上限８３０ｎｍ。对几种较重要反应产物的辐射时间变化进行了研究，发现铝粉的加入提高了己烷的反应特性，确定了几种反应产物光辐射出现的可能顺序为：Ｃ２、ＣＨ、ＣＨ２Ｏ、ＣＨＯ、ＯＨ、Ｈ２Ｏ、ＣＯ２，并对己烷快速反应点火机理进行了初步分析。     

乙醇燃烧着火延迟时间和CO2演化过程测量

本文利用激波管测量了高温条件下乙醇/氧气/氩气混合气的着火延迟时间,并结合激光吸收光谱技术测量了乙醇燃烧过程中CO₂的演化过程。本文对比了测量的着火延迟时间和3种动力学机理的预测结果,其中AramcoMech 3.0机理的预测结果和实验数据吻合较好。敏感性分析结果表明:3种机理中,促进乙醇着火的基元反应类似,但敏感性系数相差较大;CRECK机理中,抑制乙醇着火的最主要基元反应不同于AramcoMech 3.0机理和LLNL机理。将测量的CO₂演化过程和3种机理的预测结果进行对比,结果表明:对于当量比为0.5的混合气,AramcoMech 3.0机理和LLNL机理的预测结果相似,均和测量数据吻合较好;对于当量比为1.0的混合气,LLNL机理的预测结果和测量数据吻合较好。CO₂生成路径分析表明:基元反应CO+OH=CO₂+H是生成CO₂的最主要路径,但该反应在不同机理预测CO₂生成过程中所占的比例不同。     

激光消光法测量甲苯高温裂解的碳烟产率

建立了碳氢燃料在反射激波作用下高温裂解碳烟生成的检测系统,利用激光消光法测量了甲苯/氩气在高温条件下裂解生成碳烟的产率。实验条件：甲苯摩尔浓度0.25%和0.5%,压力约2和4 atm,温度1 630～2 273 K。获得了碳烟产率随温度、压力和燃料浓度的变化规律。碳烟产率随温度变化呈高斯分布,随着压力或浓度的增大,碳烟产率增大,碳烟产率最大达55%。产率的峰值温度随压力变化不大,但甲苯摩尔浓度从0.25%增大到0.5%时,峰值温度从1 852变为1 921 K。对比了压力为4 atm,燃料摩尔浓度为0.5%的甲基环己烷和甲苯的碳烟产率,甲基环己烷裂解碳烟产率峰值对应的温度为2 045 K,比甲苯约高135 K,但其最大碳烟产率仅有甲苯的1/8。结果为研究发动机内碳烟颗粒物排放及碳烟形成机理提供了实验依据。     

Experimental study of cyclohexane and methylcyclohexane oxidation at low to intermediate temperature in a motored engine

This work concerns the oxidation of cyclohexane and methylcyclohexane in a motored engine at low to intermediate temperatures, which is largely unknown in the literature. The experiment is conducted with variable compression ratio from 4 to 15 at equivalence ratio 0.25 and intake temperatures of 120 °C and 200 °C. Results show that overall reaction activity, indicated by fuel conversion and carbon monoxide formation, is largely enhanced by the existence of the methyl group. Cyclohexane shows a stronger negative temperature coefficient (NTC) behavior than methylcyclohexane. Detailed product analyses reveal that conjugated olefins are the major product for cyclohexane and methylcyclohexane in both low temperature oxidation and NTC regime. Four C₆ oxygenates, 5-hexen-1-al, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane, and cyclohexanone are detected in cyclohexane oxidation. The relative yields indicate that intramolecular hydrogen abstraction of cyclohexylperoxy radical is more likely to occur on γ-carbons than on α-, β-, or δ-carbons. Four conjugated olefins, 1-, 3-, 4-methylcyclohexenes and methylenecyclohexane, are detected in methylcyclohexane oxidation, with relative yield about 1, 1.2, 1.4 and 0.25, respectively.     

Proton N.M.R. of trismethylenemethaneiron tricarbonyl in a nematic liquid crystal

Single crystals of the cycloadduct of 1-(9-anthryl)-3-(1-naphthyl)propane (CANP) have been prepared, enabling a photochemical and photophysical study to be made of the anthracene-naphthalene sandwich pair in this material. The low temperature fluorescence spectrum is broad, exciplex in nature, and has a decay time of about 80 ns. This emission is quenched as the temperature is raised by a process which involves photocyloaddition of the pair. Arrhenius plots give an activation energy of about 600 cm^-1 for the photochemical process. The analogous photophysical properties have also been studied in methylcyclohexane glasses at 77 K and 60 K. Formation of the sandwich pairs at 77 K gives rise to a ‘ partially relaxed ’ pair having some structure in its emission spectrum and a shorter lifetime. Possible reasons for the differences in properties of sandwich pairs in methylcyclohexane glasses and the parent cycloadduct crystals are discussed. Very weak emission from the naphthalene moiety of monomer ANP has been observed at 77 K.     

Ignition behavior of pure and blended methyl octanoate,n-nonane,and methylcyclohexane

Excited-state species profiles and ignition delay times were obtained under dilute conditions (99% Ar) using a heated shock tube for methyl octanoate (C₉H₁₈O₂), n-nonane (n-C₉H₂₀), and methylcyclohexane (MCH) over a broad range of temperature and equivalence ratio (? = 0.5, 1.0, 2.0) at pressures near 1 and 10 atm. Measurements were then extended to include two ternary blends of the fuels using 5% and 20% (vol.) of the methyl ester under stoichiometric conditions. Using three independently validated chemical kinetics mechanisms, a model was compiled to assess the influence of methyl ester concentration on ignition delay times of the ternary blends. Under near-atmospheric pressure, ignition delay times were of the following order for the pure fuels: methyl octanoate < n-nonane < methylcyclohexane. Experimental results indicate that the ignition behavior of the higher-order methyl ester approaches that of the higher-order linear alkane with increased pressure regardless of equivalence ratio. Methyl octanoate also displayed significantly lower pressure dependence relative to the linear alkane and the cycloalkane species. Both of these results are supported by model calculations. Blending of methyl octanoate with n-nonane and methylcyclohexane impacted ignition delay time results more strongly at 1.5 atm, yet had only a small effect near 10 atm for temperatures above 1400 K. The study provides the first shock-tube data for a ternary blend of a linear alkane, a cycloalkane, and a methyl ester. Ignition delay time measurements for the C₉:0 methyl ester were also measured for the first time.     

Structural effects on intramolecular exciplexes of 1-amino-3-anthryl-(9)-propanes

The photophysical behavior of six 1-(N-aryl-N-alkyl)-amino-3-anthryl-(9)-propanes was studied by steady-state and time-resolved fluorescence measurements in methylcyclohexane/ isopentane (MP). Structurally, these compounds are most suitable for the formation of intramolecular exciples as shown by the high exciplex quantum yields. The rate constants and the activation energies show that the rate of the exciplex formation depends on steric effects of the N-alkyl group and on the donor effect of the N-aryl group. From the rise curves of the exciplex emission it follows that also in nonpolar solvents exciplexes with a conformation deviating from the favored sandwich structure can be formed. The solvent effect on the fluorescence properties was investigated.     

Conformational stability from Raman spectra,r0 structural parameters,and vibrational assignment of methylcyclohexane

The Raman spectra (3500–50 cm⁻¹) of the liquid and solid methylcyclohexane and the infrared spectra of the gas and solid methylcyclohexane have been recorded. The Raman band at 754 cm⁻¹ in the liquid has been confidently assigned to the less stable axial conformer and its intensity was recorded as a function of temperature from 25 to −95 °C. By the utilization of 15 different temperatures, the enthalpy difference between the more stable chair‐equatorial conformer and the chair‐axial form was determined to be 712 ± 71 cm⁻¹ (8.50 ± 0.84 kJ/mol). The ab initio predicted value of 710 cm⁻¹ (8.50 kJ/mol) from the MP2(full)/6‐311G(2d,2p) calculations with and without diffuse functions is in excellent agreement. The harmonic force fields, infrared intensities, Raman activities, depolarization ratios, and vibrational wavenumbers have been obtained for both conformers from MP2(full)/6‐31G(d) ab initio calculations. With two scaling factors of 0.88 for the C‐H stretches and 0.9 for the remaining ones, the fundamental wavenumbers have been predicted and along with the depolarization values and infrared band contours (B‐type for A″ modes) a complete vibrational assignment has been made for the chair‐equatorial conformer. Predicted r₀ structural parameters have been provided from adjusted parameters from ab initio MP2(full)/6‐311+G(d,p) calculations. The results are discussed and compared with the corresponding properties of some similar molecules. Copyright © 2009 John Wiley & Sons, Ltd.     

Evaluation of the parameters of electron transport in liquid hydrocarbons using the photoconductivity technique

The ballistic model of electron transport proposed by Mozumder (Chem. Phys. Lett. 1993. V. 207. P. 245) is applied to interpret experimental data on the photoconductivity of solutions in three hydrocarbon liquids: methylcyclohexane, isooctane, and squalane. For methylcyclohexane, the values of the quasi-free electron mobility 100 cm² V^?1 s^?1 and electron trap density 3 · 10¹⁹ cm^?3 agree with experimental data. For isooctane, the motion of a quasi-free electron is nearly diffusive, whereas the trap density is ～0.8 · 10¹⁸ cm^?3. As to squalane, the two-state model turned out to be inapplicable to describing electron transport. The results obtained are used to discuss initial stages of ionization in liquids.     

Non-invasive determination of shock wave pressure generated by optical breakdown

Shock waves generated by a laser-induced plasma were investigated using a pump-and-probe technique. Both 7-ns and 40-ps laser pulses at 1.06 m were employed to initiate breakdown in water. Two He-Ne laser beams were used as a velocity probe, allowing the accurate measurement of the shock velocity around the plasma. The maximum shock pressure was determined from the measured shock velocities, the jump condition and the equation of state for water. The conservation of the total momentum of the shock front was used to derive expressions for the shock velocity, particle velocity and shock pressure vs. the distance (r) from the center of the plasma. For a shock wave of spherical symmetry, the shock pressure is proportional to 1/r ². Our work shows that the expanding plasma initially induces a shock wave; the shock wave dissipates rapidly becoming an acoustic wave within 300–500 m.